An efficient TEMPO鈥揳ir/cat. TEMPO鈥揙2 oxidative protocol was developed to synthesize multisubstituted or fused tetracyclic benzimidazoles via a metal-free oxidative C鈥揘 coupling between the sp3 C鈥揌 and free N鈥揌 of readily available N1-benzyl/alkyl-1,2-phenylenediamines.